The nature of the short wavelength excitations in vitreous silica: X-Rays Brillouin scattering study

The dynamical structure factor (S(Q,E)) of vitreous silica has been measured by Inelastic X-ray Scattering varying the exchanged wavevector (Q) at fixed exchanged energy (E) - an experimental procedure that, contrary to the usual one at constant Q, provides spectra with much better identified inelastic features. This allows the first direct evidence of Brillouin peaks in the S(Q,E) of SiO_2 at energies above the Boson Peak (BP) energy, a finding that excludes the possibility that the BP marks the transition from propagating to localised dynamics in glasses.Comment: 4 pages, 3 Postscript figures. To appear in Physical Review Letter

Vibrational spectrum of topologically disordered systems

The topological nature of the disorder of glasses and supercooled liquids strongly affects their high-frequency dynamics. In order to understand its main features, we analytically studied a simple topologically disordered model, where the particles oscillate around randomly distributed centers, interacting through a generic pair potential. We present results of a resummation of the perturbative expansion in the inverse particle density for the dynamic structure factor and density of states. This gives accurate results for the range of densities found in real systems.Comment: Completely rewritten version, accepted in Physical Review Letter

Acoustic Nature of the Boson Peak in Vitreous Silica

New temperature dependent inelastic x-ray (IXS) and Raman (RS) scattering data are compared to each other and with existing inelastic neutron scattering data in vitreous silica (v-SiO_2), in the 300 - 1775 K region. The IXS data show collective propagating excitations up to Q=3.5 nm^-1. The temperature behaviour of the excitations at Q=1.6 nm^-1 matches that of the boson peak found in INS and RS. This supports the acoustic origin of the excess of vibrational states giving rise to the boson peak in this glass.Comment: 10 pages and 4 figure

Combining Raman and infrared spectroscopy as a powerful tool for the structural elucidation of cyclodextrin-based polymeric hydrogels

A detailed experimental and theoretical vibrational analysis of hydrogels of b-cyclodextrin nanosponges (b-CDNS), obtained by polymerization of b-cyclodextrin (b-CD) with the cross-linking agent ethylenediaminetetraacetic acid (EDTA), is reported here. Thorough structural characterization is achieved by exploiting the complementary selection rules of FTIR-ATR and Raman spectroscopies and by supporting the spectral assignments by DFT calculations of the spectral profiles. The combined analysis of the FTIR-ATR spectra of the polymers hydrated with H2O and D2O allowed us to isolate the HOH bending of water molecules not involved in symmetrical, tetrahedral environments. The analysis of the HOH bending mode was carried out as a function of temperature, showing the existence of a supercooled state of the water molecules. The highest level of cooperativity of the hydrogen bond scheme was reached at a value of the b-CD/EDTA molar ratio n = 6. Finally, the connectivity pattern of ‘‘uncoupled’’ water molecules bound to the nanosponge backbone was found to be weakened by increasing T. The temperature above which the population of non-tetracoordinated water molecules becomes predominant turned out to be independent of the parameter n

Low-frequency dynamics of disordered XY spin chains and pinned density waves: from localized spin waves to soliton tunneling

A long-standing problem of the low-energy dynamics of a disordered XY spin chain is re-examined. The case of a rigid chain is studied where the quantum effects can be treated quasiclassically. It is shown that as the frequency decreases, the relevant excitations change from localized spin waves to two-level systems to soliton-antisoliton pairs. The linear-response correlation functions are calculated. The results apply to other periodic glassy systems such as pinned density waves, planar vortex lattices, stripes, and disordered Luttinger liquids.Comment: (v2) Major improvements in presentation style. One figure added (v3) Another minor chang

The crossover from propagating to strongly scattered acoustic modes of glasses observed in densified silica

Spectroscopic results on low frequency excitations of densified silica are presented and related to characteristic thermal properties of glasses. The end of the longitudinal acoustic branch is marked by a rapid increase of the Brillouin linewidth with the scattering vector. This rapid growth saturates at a crossover frequency Omega_co which nearly coincides with the center of the boson peak. The latter is clearly due to additional optic-like excitations related to nearly rigid SiO_4 librations as indicated by hyper-Raman scattering. Whether the onset of strong scattering is best described by hybridization of acoustic modes with these librations, by their elastic scattering (Rayleigh scattering) on the local excitations, or by soft potentials remains to be settled.Comment: 14 pages, 6 figures, to be published in a special issue of J. Phys. Condens. Matte

The Raman coupling function in amorphous silica and the nature of the long wavelength excitations in disordered systems

New Raman and incoherent neutron scattering data at various temperatures and molecular dynamic simulations in amorphous silica, are compared to obtain the Raman coupling coefficient $C(\omega)$ and, in particular, its low frequency limit. This study indicates that in the $\omega \to 0$ limit $C(\omega)$ extrapolates to a non vanishing value, giving important indications on the characteristics of the vibrational modes in disordered materials; in particular our results indicate that even in the limit of very long wavelength the local disorder implies non-regular local atomic displacements.Comment: Revtex, 4 ps figure

The evolution of vibrational excitations in glassy systems

The equations of the mode-coupling theory (MCT) for ideal liquid-glass transitions are used for a discussion of the evolution of the density-fluctuation spectra of glass-forming systems for frequencies within the dynamical window between the band of high-frequency motion and the band of low-frequency-structural-relaxation processes. It is shown that the strong interaction between density fluctuations with microscopic wave length and the arrested glass structure causes an anomalous-oscillation peak, which exhibits the properties of the so-called boson peak. It produces an elastic modulus which governs the hybridization of density fluctuations of mesoscopic wave length with the boson-peak oscillations. This leads to the existence of high-frequency sound with properties as found by X-ray-scattering spectroscopy of glasses and glassy liquids. The results of the theory are demonstrated for a model of the hard-sphere system. It is also derived that certain schematic MCT models, whose spectra for the stiff-glass states can be expressed by elementary formulas, provide reasonable approximations for the solutions of the general MCT equations.Comment: 50 pages, 17 postscript files including 18 figures, to be published in Phys. Rev.

Elastic constant dishomogeneity and Q2Q^2 dependence of the broadening of the dynamical structure factor in disordered systems

We propose an explanation for the quadratic dependence on the momentum $Q$, of the broadening of the acoustic excitation peak recently found in the study of the dynamic structure factor of many real and simulated glasses. We ascribe the observed $Q^2$ law to the spatial fluctuations of the local wavelength of the collective vibrational modes, in turn produced by the dishomegeneity of the inter-particle elastic constants. This explanation is analitically shown to hold for 1-dimensional disordered chains and satisfatorily numerically tested in both 1 and 3 dimensions.Comment: 4 pages, RevTeX, 5 postscript figure

Inelastic light, neutron, and X-ray scatterings related to the heterogeneous elasticity of glasses

The effects of plasticization of poly(methyl methacrylate) glass on the boson peaks observed by Raman and neutron scattering are compared. In plasticized glass the cohesion heterogeneities are responsible for the neutron boson peak and partially for the Raman one, which is enhanced by the composition heterogeneities. Because the composition heterogeneities have a size similar to that of the cohesion ones and form quasiperiodic clusters, as observed by small angle X-ray scattering, it is inferred that the cohesion heterogeneities in a normal glass form nearly periodic arrangements too. Such structure at the nanometric scale explains the linear dispersion of the vibrational frequency versus the transfer momentum observed by inelastic X-ray scattering.Comment: 9 pages, 2 figures, to be published in J. Non-Cryst. Solids (Proceedings of the 4th IDMRCS